1,3-dithietane - 2,2,4,4 - tetraacyl chloride and the corresponding ester and amide derivatives



United States Patent O 1,3-DITHIETANE 2,2,4,4 TETRAACYL CHLORIDE AND THECORRESPUNDING ESTER AND AMIDE DERIVATIVES Robert A. Grimm, Lakeville,Minn, assignor to Ashland Oil & Refining Company, Ashland, Ky., acorporation of Kentucky No Drawing. Continuation-impart of applicationSer. No. 466,110, June 22, 1966. This application Mar. 19, 1968, Ser.No. 716,699

Int. Cl. C0711 69/00; C07c 153/05 US. Cl. 260327 7 Claims ABSTRACT OFTHE DISCLOSURE Carbon suboxide is reacted with sulfur dichloride toyield l,3-dithietane-2,2,4,4-tetraacyl chloride or reacted with ahydrocarbylsulfenyl chloride to yield a malonyl chloride. Said tetraacylchloride or malonyl chloride can be hydrolyzed with an alcohol to forman ester or reacted with ammonia or a primary or secondary amine to forman amide. The tetraacyl chlorides of this invention as Well as theirester and amide derivatives are useful as monomers in the preparation ofpolyesters for film-forming coatings. Additionally, said esters andamides possess utility as plasticizers for polyvinyl chloride.

This application is a continuation-impart of my copending applicationSer. No. 466,110, filed June 22, 1966, and now abandoned.

This invention relates to the preparation of1,3-dithietane-2,2,4,4-tetraacyl chloride, and its corresponding esterand amide derivatives, as new compounds. In another aspect, it relatesto the preparation of hydrocarbylthio malonyl chlorides, and theircorresponding ester and amide derivatives, as new compounds.

Briefly, I have discovered a new class of compounds having the GeneralFormulas A and B:

i where R is a member selected from the group consisting of chlorine,OR", and N(R) where R" is an alkyl, alkenyl, or substituted alkyl ester(such as ester substituted alkyl), R generally having 1 to 20 carbonatoms, and R'" is a hydrocarbyl radical, generally having 1 to 18 carbonatoms, such as alkyl, cycloalkyl, aryl, and combinations thereof such asalkaryl, aralkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl,cycloalkylaryl, and the like. R' is preferably an alkyl or aryl. R'" canhave various functional groups or substituents, such as chloro and estergroups, though I prefer that R be an unsubstituted hydrocarbyl radical,that is, that it consist only of hydrogen and carbon atoms.

The acyl chloride of General Formula A (i.e., where R is chlorine) isprepared according to this invention by reacting stoichiometric amountsof sulfur dichloride and carbon suboxide as illustrated by the followingreaction:

1, 3-dithietane-2, 2, 4, 4- tetraaeyl chloride ice The carbon suboxidereactant can be prepared by a variety of methods, though I prefer toprepare it by pyrolysing diacetyl tartaric anhydride, condensing theresulting vaporous carbon suboxide, and maintaining it in its liquidstate prior to use by keeping it below its boiling point (7 C.). Theliquid carbon suboxide can then be mixed with a solution of the sulfurdichloride in an inert solvent such as ethyl ether, carbontetrachloride, toluene, chloroform, xylene, cyclohexane, or one of theFreons. The mixing of the reactants together is preferably carried outat a temperature in the range of 80 to 0 C., preferably 20 to 0 C., bydistilling the carbon suboxide into the sulfur dichloride solution. Thereaction vessel is then closed to prevent escape of the carbon suboxide.The ensuing reaction is preferably maintained at a temperature in therange of 25 C. to 7 C. As the reaction proceeds, and while it ismaintained at said low temperatures, 1,3-dithietane-2,2,4,4-tetraacylchloride forms and generally precipitates as orange crystals, thereaction or precipitation generally being complete in 1 to 5 hours.Recovery of the product can be accomplished by several known recoverytechniques, for example, by filtering off the crystals and washing themwith further solvent, such as hexane, and then drying the crystalproduct. If the product is soluble in the solvent, the solution can beused as is to prepare further derivatives or else the solvent can beremoved and the solid product recovered.

The malonyl chlorides of the compounds having General Formula B can beprepared by reacting stoichiometric amounts of a hydrocarbylsulfenylchloride,

where R'" is as defined above, with carbon suboxide according to thegeneral reaction:

' f RS d-Cl 2RSCl o=o=c=o=o 0 RS (IIJ-OI 0 (II) In other respects,Reaction II is carried out in the manner described above for Reaction I.The products of Reaction II can be similarly recovered and, where asingle sulfenyl chloride reactant is used rather than a mixture ofdifferent sulfenyl chlorides, the products are named2,2-bis(hydrocarbylthio)-malonyl chlorides. Where a mixture of difierentsulfenyl chlorides are used, the products are named as2-hydrocarbylthio-2-hydrocarbylthiomalonyl chlorides.

Representative hydrocarbylsulfenyl chlorides which can be used incarrying out Reaction -II representatively in clude inethanesulfenylchloride, ethanesulfenyl chloride, propanesulfenyl chloride,hexanesulfenyl chloride, propanesulfenyl chloride, hexanesulfenylchloride, octanesulfenyl chloride, decanesulfenyl chloride,dodecanesulfenyl chloride, tridecanesulfenyl chloride,tetradecanesulfenyl chloride, 'hexadecanesulfenyl chloride,octadecanesulfenyl chloride, Z-methlyl-Z-propanesulfenyl chloride,chloromethanesulfenyl chloride, carboethoxymethanesulfenyl chloride,cyclohexanesulfenyl chloride, l-chlorocyclohexanesulfenyl chloride,para-toluenesulfenyl chloride, alphatoluenesulfenyl chloride,2-methylcyclohexanesulfenyl chloride, cyclohexylmethanesulfenylchloride, 4-phenylcyclohexanesulfenyl chloride,4-cyclohexylbenzenesulfenyl chloride, and the like, including mixturesthereof.

Representative 2,2-bis(hydrocarbylthio) malonyl chlorides which can beprepared according to this invention include 2,2-bis(methylthio)malonylchloride, 2,2-bis(eth ylthio )malonyl chloride, 2,2-bis(octadecylthio)malonyl chloride, 2,2-bis(2-rnethyl-2-propylthio) malonyl chloride,2,2-bis(chloromethylthio) malonyl chloride,2,2-bis(carboethoxymethylthio) malonyl chloride, 2,2.-bis(cyclohex- Y hlo r th -'ride and the; lik

. octyL alcohol;

1.3-p' Pa dio.

ylthio) malonyl chloride,j2,2-bis(1-chlorocyclohexylthio).malonylehloride,- 2,2-bis(paratolylthio)malonyl chloride, 2,2bis(alpha-tolylthio) ,malonyl chloride, 2,2vbis(2-meth- Q lylcyclohexylthio malonylchloride, 2,-2fbis(cyclohexyl-.

Tylthio) malonylohloride, 2,-2 bjs 'cyclohexylphenylthio)malonyl.clrloride, I-Z-phenylthio 2amethylthiomalonyl chloride, :2paraetolylthio-Z-octadecylthiomalo'nyl chlo'ride'yZ-l"2-carboethoxyrnethylthiomalonyl 611 10.

t a 9 ,of GeneralForinnlasfA and B,1i.e., the illustrated reaction;

"products;of1 Reactions;Iiand II, jrespective1y, tcan be used to!prepare the corresponding ester. and amide derivatives.

; jInQf rmingEthe ester derivativesfthe"chloride" precursor is &{hydrolyzed with a monogjorl polyhydric falcohol;.or. ester substitntedalcohols, particularlyfthose, of the. latter dea 1, rived fromathehigherffatty acids. Representative alcohols .which. can be; usedincliideQethylIalcohol ybutyl alcohol,';i

ctadee'ylf'alcohol,,i9 octadecenyl aleohol, i f ,ethyl19;hydroxystearate, ethyl IZ-hy d' o yst a te. m h .8 -h Q y t a te; tL'l-o a bi r-. "anedio l, pentaerythritol," and'the like, includingmixtures Y thereof. ,Representatively, estersjof theQchloridesofGenQ t jeral Formula A {include i di-l2('ethylsteareateldimethyl l,3-;dithietane;-;2,2,4Atetracarboxylate; di-18-(ethylstear4 ate)diethyl1,3-dithietane2,2,4,4-tetracarboxylate, diethyl' i dioctadecyl LS-dithftape-2,2,4,4etetracarboxylate,ftetraflfl ethyL1,3 -diethietane2 2,2,4,4-tetracarboxy1ate, tetra'botyl 3 i I 1Q3idithietanef2,2,4,4-tetracarboxylate, ftenaoctadecyl 1,3,dithietane"5,2,2,4,4-tetracarboxylate,tetra (9;octadecenyl) [1;3 1 thfi e ,2,4; aa QXy e. Z-( hY stearate)*l,3r-dithietane2,2,4At-tetracarhoxylaie,"andthe' 1 like, and the'polyesters, resulting,fromreactionlwith 1,3 propanediol, octadecanediol'arid pentaerythritol;The simplea tetra-esters ,(i.e., those; resulting from hydrolysis of jester andamide derivatives, are *useful' as monomers in a V e V thepreparation of "polyesters for film-formingcoatings, f v the' p n of Genral FormulaB i d llf jarldcanalsobe used as chemical intermediatesinorganic 2,2 bis(phenylthio) ,ina1onate,dibutyl 2,2-bis(chloromethi ITylthio),{-malonate, .cyclohexyl octadecylj2,2 bis(chloro a methylthio);flrnalonate, "di-12- (ethylstearate) 2,2,bisf

(alpha tolylthio) malonate, dioctadecyl r2,2-bis(methyl .11 fthio)jmalonate, dirriethylj2,2-bis'(methylthio) malonate, l 1 1,3vp rlopanediol,and polymers resulting from 1 reaction V the Chloriddprebursor witlrfiafmon'o-h ydric alcohol):arensefulasplasticizers;Representativeestersofthe chlorides with,octadecanediolwand pentaerythritol z 1.'lhe;estersof these "acidhloridesof GeneralFor'rnnlas fliuking agents for polyester resins Forexample, hydroxyl- Aj andf B, elg., esters of methyl through eicosylalcohols 3 and unsaturated and ester substituted alcjoholsi as; well asI the amides of the ;corresponding; amineslof said "alcohols,

1 "are useful as "plasticizers for ;poly(vin yl chloride) Addi- -tionofthese compounds, eig qtetradodecyl 1,3:dithietane;

2,2,4,4-tetracarboxylate, to. poly vinyl chloride) inja coni I.ventional manner at a concentration of from 3-15 p.p.h.

toluene, eta, should be-usedto dissolve such solids. Reaction of:thechloridesof thecompounds" of General Forf mIIlas ZAand B with the;alcohols can be carried out at L I roomftemperaturel( 25 C.) althoughtemperatures 'in the broad-range of --.1Qfto 609C. areapplicable; At"room alyst is necessary. l

it The amidefderivatives offlthei' chlorides of theicom o o .odor andamelting point of 79-82 C. This crystal prodpoundsof General FormulasandB can be'preparedby 1 jreacting the chloridefpreeursor with ammoniaor primary or:seoondaryQaminesIAmines which can be used for this a "4purpose, representatively include ammonia,methyla'mine, .dunethylamine,ethylamine, diethylamine, octylamine,

,tures thereof. Representative amides of the chlorides of f carboxamide, ,tetra-(N-ethyl) 1,3 dithietane 2,2,4,4-tetracarboxamide, di-(Nethyl),-di-(N-octadecyl) 1,3-dithiet- "ane 2,2,4,44etracarboxamide,,tetra-(N-octadecyl) 1,3-di- 1,3-dithietane 2,2,4,4-tetracarboxamide,tetra+9-(N-ethylf stearate) 1,3-dithietane-2,2,4;4-tetracarboxamide,tri-(N- 'inethyD-N-octadecyl:1,3-dithietane 2,2,4,4-te tracarboxamide,-1,3-dithietane- 2,2,4,4tetracarboxanilide, di-(N- 15@phenYll-di-(Ngoctyl) -2,2,4,4 'tetracarboxamide, tetra- (N,N-diethyl)l,3'-dithietane 2,2 ,4,4 tetracarboxamide, and the like. Representativesof the amides of General Formula 3 include,2,2-bis(phenylthio)malonamide, N- phenyl-Nf-octadecyL, malonamide,2,2-bis (methylthio) f7malonanilide, di -N-ethyl 2,2-bis(benzylthio)malonamide, I e

' di-N,N-'diethyl 2 ,'2-bis(benzylthioymalonamide, and the like. r *Theamide derivatives oftheIacyl chlorides of the comrides are-then added tothe solution of ammonia or amine catalysts.

" of these amides can be accomplished without theme of The acylchlorides of this-invention, aswell as their as jl;10-decanedi ol or.l,9 (1l0)o ctadec anediol and. subse- 45, "butylamin'egives apolymerfrom which films can be cast qacyl chloride, and malonylchlorides are useful as crosscontaining polyester resins such as thoseobtained from triglycerides (e.g., linseed oil), glycerol anddiacidanhydrides (e.g., phthalic anhydride), upon mixi'ngwith-thestood'thatithe particular reactants, conditions of the reac tion, andother. details of these examples should not be I construedto undulylimit this invention; a

a EXAMPLEII':

- solution of freshly distilled sulfur dichloride (0.835

fjmole) in ethyl ether (10 molesJ was mixed with a 'solution of carbonsuboxidef (0.82 mole) in ether (20 moles) r atOf C. The reaction flask'wastightly'stoppered and not was .characterized a's'1,3-dithietane-2,2,4,4-tetraacyl 75. chloride by making thecorresponding ethyl ester and I ftetradecylamine, octadecylamine,9-octadecenylamine,

Y ethyl 9-aminostearate, aniline, and the like, including mixgeneralformula A include '1,3-'dithietane 2,2,4,4-tetrae e p e p 0 ,thietane2,2,4,4-tetracarboxamide,tetra-(N-9 octadecenyl)- Thefchlorides of the.co'rlnponndsjjfalling the scope} I r j pounds of General Formulas A andB can betprepared' 01 decomposition and should be avoided.) Theacyl-chlo-' with stirring, the acyl chloridereactant being preferablydissolved in one: of said inert solvents. The; preparation asynthesesJFor example, reaction of one mole of the tetra-- .acylchloridewith one mole; of a dihydroxy alcoholsuch E quent reaction of thisproduct withtwo moles of a mono-' h'ydroxyl alcohol or amine such asethylhexanol or di-nby ordinary 'techniques.- The 1,3dithietane-2,2,4,4-tetra-' aforementioned acyl chloridesin an iountssutlicient to re-' act with remaining. hydroxyl groups of said polyesterL s 7 e resin, andimmediate applicationlof the mixture of polyan -mil lj a ie zei.p ly( ny l id 55- ester resinandqacid chloridefto "a surfaceresults in a i A? {If amixtureof alcohols is used tojp'repareithe esteride-.

"r'ivatives of "this ir'ivention, *such derivatives willhavedifierentester groups, i.e'.,-different OR. groups will be; attached to thecarbonfatomsfoffthe various carbonyl". qgroups of the co'mpoundsof'GeneralFormulas A and B. Hffthehlcoholsused to prepareftheesterderivatives are Y zliqu'ids, the esters?=can be made bysimple-addition of the fl alcoholfto}the acy1,chlorideAHowever,thea'lcohols are' solids, inerta'solvents such as'chloroforrn, benzene,

Y storedin a freezer at ZS? C. until the, resultingorange temperature,the re cti'on is 'alniostinstaneous and no cat-I 70, .prismsstoppedgrowing, the crystals 'were filtered from diethyl amine derivatives, asdescribed in the following examples.

EXAMPLE II One and two-tenths moles of the crystal product of Example Iwere mixed with about 6 moles of ethyl alcohol. A vigorous reactionensued forming an odorless, yellow solution. A small excess of the ethylalcohol was removed from the reaction product, causing the oil tocrystallize. The crystal product was decolorized with activated charcoaland upon recrystallizing it with hexane was found to have a meltingpoint of 59.5 to 60 C. Elemental analysis, infrared spectrum analysis,nuclear magnetic resonance and molecular weight determinationestablished the product as tetraethyl-l,3-dithietane-2,2,4,4-tetracarboxylate.

EXAMPLE III Six-tenths mole of the crystal product of Example I wasdissolved in ether at room temperature and moles of diethyl amine wereadded to the solution until it became alkaline. The resultingprecipitate that was formed was filtered and found to be diethylammonium chloride. The ether was evaporated from the filtrate, producinga brown oil that was triturated with hexane. The remaining material wasthen recrystallized from hexane-acetone to give colorless prisms, M.P.194.5195 C., which was characterized by infrared spectrum analysis asN,N-diethyl-l,3-dithietane-2,2,4,4-tetracarboxamide.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention, and it should be understood that thisinvention is not to be unduly limited to that set forth herein forillustrative purposes.

6 What is claimed is: 1. A compound having the general formula 0 0 II IIR'C s CR R- |.|J s (?R 0 l) where R is a member selected from the groupconsisting of chlorine, OR, and N(R") where R is a C -C alkyl or C -Calkenyl radical.

2. A compound according to claim 1 where R is chlorine.

3. A compound according to claim 1 where R is OR", and R is a C -C alkylor C -C alkenyl.

4. A compound according to claim 1 where R is N(R") and R" is a C -Calkyl or C -C alkenyl.

5. A compound according to claim 3 where R is OCH CH 6. A compoundaccording to claim 4 where R is --N (CH CH 7. A process of preparing thecompound of claim 2 which comprises reacting at a temperature betweenabout 25 C. and 7 C. carbon suboxide with sulfur dichloride andrecovering the resultant product.

References Cited UNITED STATES PATENTS 3,113,936 12/1963 Middleton 260793,117,977 1/1964 Middleton 260-327 HENRY R. JILES, Primary Examiner C.M. SHURKO, Assistant Examiner US. Cl. X.R.

